CN1946796A - Thermoplastic elastomer composition - Google Patents
Thermoplastic elastomer composition Download PDFInfo
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- CN1946796A CN1946796A CNA2005800129100A CN200580012910A CN1946796A CN 1946796 A CN1946796 A CN 1946796A CN A2005800129100 A CNA2005800129100 A CN A2005800129100A CN 200580012910 A CN200580012910 A CN 200580012910A CN 1946796 A CN1946796 A CN 1946796A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
Abstract
The invention provides a thermoplastic elastomer composition which is excellent in light resistance and flexibility and has high tear strength. A thermoplastic elastomer composition comprising 100 parts by mass of acrylic multi-layer polymer particles (A) which each comprise at least two layers, i.e., at least one inner rubber layer (I) and at least one outermost thermoplastic resin layer (II), 5 to 300 parts by mass of an ethylene/vinyl ester copolymer (B), and 0.5 to 150 parts by mass of a graft copolymer (C) composed of an ethylene/vinyl ester copolymer backbone and a graft bonded to the backbone which consists of units derived from a monomer having a polarity higher than that of the backbone.
Description
Technical field
The present invention relates to contain specific acrylic acid series multilayer structure polymer particle, ethylene vinyl acetate copolymer (エ チ レ Application-PVC ニ Le エ ス テ Le copolymer) and specific graft copolymer, photostabilization, flexibility are good, and can access the composition for thermoplastic elastomer of the big film of tear strength.
Background technology
Acrylic resin not only has good photostabilization, and have the beautiful outward appearance and a transparency, also be shaped easily, so be widely used in electrical component, vehicle part, optics with purposes such as parts, ornament, billboards, people are studying and how are further improving its performance in order to enlarge its purposes.Wherein, in recent years, in recognizing thin thing molding purposes such as the film that reduces cost or thin slice, owing to there is when burning away the refuse problems such as environment being produced load, people are in the research of carrying out energetically acrylic resin, to replace flexible vinyl chloride-based resin.But present situation is an acrylic resin hardness height, and therefore the use limitation is expected to it is improved.As this improvement, known have a kind ofly do not need directly to use the high acrylic resin of hardness as shaping raw material, film that is made of acrylic acid series multilayer structure polymer particle or thin slice are (for example, refer to Patent Document 1,2), but the film of document record is only to be shaped by acrylic acid series multiple layer polymer particle to obtain, and has the problem of tear strength difference.In addition, the known thermoplastic polymer composition that acrylic acid series multiple layer polymer mix particles is formed to various thermoplastic polymers, but still there be not the improvement of realization to the film tear strength.(for example, referring to Patent Document 3).
Patent documentation 1: the spy opens clear 58-215443 communique
Patent documentation 2: the spy opens clear 59-86650 communique
Patent documentation 3: the spy opens flat 9-216967 communique
Summary of the invention
The technical problem that invention will solve
The purpose of this invention is to provide photostabilization, flexibility is good, and can access the composition for thermoplastic elastomer of the big film of tear strength.
The technical scheme of dealing with problems
The inventor etc., various researchs have been carried out in order to address the above problem, found that the composition for thermoplastic elastomer that contains acrylic acid series multilayer structure polymer particle, ethylene vinyl acetate copolymer (エ チ レ Application-PVC ニ Le エ ス テ Le copolymer) and specific graft copolymer can address the above problem, thereby finished the present invention.
That is, the present invention relates to
(1) composition for thermoplastic elastomer, contain acrylic acid series multilayer structure polymer particle (A) 100 mass parts, ethylene vinyl acetate copolymer (B) 5～300 mass parts, and on the main chain that constitutes by ethylene vinyl acetate copolymer grafting be higher than graft copolymer (C) 0.5～150 mass parts that the monomeric unit of this main chain forms in conjunction with polarity, wherein
(a) this acrylic acid series multilayer structure polymer particle (A) is, has at least 1 layer of rubber constituent layer (I) by inside, and outermost layer has at least 1 layer of thermoplastic resin component layer (II), and such layer more than 2 layers constitutes,
(b) this rubber constituent layer (I) is, the polymer layer that forms by acrylate 50～99.99 quality %, the monomer mixture (i) that can constitute by copolymerization with other monofunctional monomers 49.99～0 quality % and polyfunctional monomer 0.01～10 quality % of this acrylic ester copolymer
(c) this thermoplastic resin component layer (II) is, the polymer layer that (ii) forms by methacrylic ester 40～100 quality % and the monomer that can constitute by polymerization with other monomer 60～0 quality % of this methacrylic ester copolymerization,
(d) in this thermoplastic resin component layer (II), the number-average molecular weight of the outermost layer polymkeric substance of measuring with the GPC method is below 30,000,
(e) ratio [(I)/(II)] of the total quality of the total quality of this rubber constituent layer (I) and this thermoplastic resin component layer (II) is 30/70～90/10,
(f) median size of this acrylic acid series multilayer structure polymer particle (A) is below the 150nm;
(2) composition for thermoplastic elastomer of above-mentioned (1) record, wherein, on the main chain of graft copolymer (C) grafting bonded monomeric unit for from (methyl) acrylic ester monomeric unit, Vinyl Ether be select monomeric unit, (methyl) acrylamide monomeric unit, the acrylic monomeric unit more than at least a kind;
(3) composition for thermoplastic elastomer of above-mentioned (2) record, wherein, grafting bonded monomeric unit is a methyl methacrylate units on the main chain of graft copolymer (C);
(4) molding that constitutes by the composition for thermoplastic elastomer of above-mentioned (1) record;
(5) film or the thin slice that constitutes by the composition for thermoplastic elastomer of above-mentioned (1) record; And
(6) has the composite molded product of the part that the composition for thermoplastic elastomer by above-mentioned (1) record constitutes.
The beneficial effect of the invention
According to the present invention, can provide photostabilization, flexibility good, and form the big composition for thermoplastic elastomer of its tear strength behind the film.
Embodiment
Below, describe for preferred implementation of the present invention, but the present invention is not limited by following explanation.
The acrylic acid series multilayer structure polymer particle (A) that uses among the present invention is that inside has at least 1 layer of rubber constituent layer (I), and outermost layer has at least 1 layer of thermoplastic resin component layer (II) (following layer (I), the layer (II) of slightly being designated as respectively sometimes).The quantity that constitutes the layer of the acrylic acid series multilayer structure polymer particle (A) that uses among the present invention is, can be more than 2 layers, can be more than 3 layers, also can be more than 4 layers.The situation of 2 layers of structure is the structure of [layer (I) (central core)/layer (II) (outermost layer)], the situation of 3-tier architecture is the structure of [layer (I) (innermost layer)/layer (I) (middle layer)/layer (II) (outermost layer)], [layer (I) (innermost layer)/layer (II) (middle layer)/layer (II) (outermost layer)] or [layer (II) (innermost layer)/layer (I) (middle layer)/layer (II) (outermost layer)], the situation of 4 layers of structure is, for example can be the structure with [layer (I) (innermost layer)/layer (II) (middle layer)/layer (I) (middle layer)/layer (II) (outermost layer)].Wherein, consider from the aspect that operability is good, preferably 2 layers of structure of [layer (I) (central core)/layer (II) (outermost layer)], the perhaps 3-tier architecture of [layer (I) (innermost layer)/layer (I) (middle layer)/layer (II) (outermost layer)] or [layer (II) (innermost layer)/layer (I) (middle layer)/layer (II) (outermost layer)].
In addition, the total mass ratio [(I)/(II)] of the layer (I) of acrylic acid series multilayer structure polymer particle (A) and layer (II) should be in 30/70～90/10 the scope.The ratio of layer (I) is during less than 30 quality %, the elastic recovery of the molding that is made of the composition for thermoplastic elastomer that obtains becomes insufficient, on the other hand, when the ratio of layer (I) surpasses 90 quality %, acrylic acid series multilayer structure polymer particle (A) is difficult to complete morphology form layers structure, melt fluidity descends greatly, waits the fusion of other compositions to mix and be shaped with ethylene vinyl acetate copolymer (B) and becomes difficult.Wherein, the total mass of layer (I), when the layer (I) in the acrylic acid series multilayer structure polymer particle (A) is the quality of this layer when only being 1 layer, when layer (I) be more than 2 layers the time be these layers each quality and.Similarly, the total mass of layer (II), when the layer (II) in the acrylic acid series multilayer structure polymer particle (A) is the quality of this layer when only being 1 layer, when layer (II) be more than 2 layers the time be these layers each quality and.The total mass ratio [(I)/(II)] of layer (I) and layer (II) is, preferably in 50/50～90/10 scope, more preferably in 60/40～90/10 scope.
The layer (I) of the acrylic acid series multilayer structure polymer particle (A) that uses among the present invention should for, by the multipolymer of acrylate 50～99.99 quality % and the monomer mixture (i) that can constitute with other monofunctional monomers 49.99～0 quality % and polyfunctional monomer 0.01～10 quality % of this acrylic ester copolymer.The proportion of composing of this monomer mixture (i), be preferably acrylate 55～99.9 quality % and can with other monofunctional monomers 44.9～0 quality % and polyfunctional monomer 0.1～2 quality % of this acrylic ester copolymer.The amount of acrylate is during less than 50 quality %, the photostabilization of the caoutchouc elasticity of acrylic acid series multilayer structure polymer particle (A) or the composition for thermoplastic elastomer that obtains descends, when surpassing 99.99 quality %, acrylic acid series multilayer structure polymer particle (A) is difficult to complete morphology form layers structure, melt fluidity descends greatly, waits the fusion of other compositions to mix with ethylene vinyl acetate copolymer (B) and becomes difficult.In addition, when the amount of polyfunctional monomer surpassed 10 quality %, acrylic acid series multilayer structure polymer particle (A) can not show caoutchouc elasticity, and it is insufficient that elastic recovery becomes, and during less than 0.01 quality %, layer (I) does not form particle structure.
Wherein, when acrylic acid series multilayer structure polymer particle (A) has layer more than 2 layers when (I), constitute the multi-functional monomeric blending ratio of the monomer mixture (i) of each layer (I), 0.01～10 quality % in principle should respectively do for oneself.
As the object lesson of the acrylate that is used to form layer (I), can enumerate vinylformic acid and C such as methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, Octyl acrylate, 2-EHA, dodecylacrylate, vinylformic acid stearyl
1～C
18The ester of saturated fatty alcohol, vinylformic acid and C such as cyclohexyl acrylate
5Or C
6The ester of ester ring type alcohol, the ester of vinylformic acid such as phenyl acrylate and phenol, the ester of vinylformic acid such as benzyl acrylate and aromatic alcohols, they can use separately or be used in combination more than 2 kinds, can according to purpose or purposes is suitable select.
As be used to form the layer (I) can with other monofunctional monomers of this acrylic ester copolymer, representative is methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid pentyl ester, N-Hexyl methacrylate, Octyl methacrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate, methacrylic acid tetradecyl ester, methacrylic acid palm ester, the methacrylic acid stearyl ester, methacrylic acid and C such as methacrylic acid docosyl ester
1～C
22The ester of saturated fatty alcohol, methacrylic acid and C such as cyclohexyl methacrylate
5Or C
6The ester of ester ring type alcohol, the ester of methacrylic acids such as phenyl acrylate and phenol, the ester of methacrylic acids such as benzyl acrylate and aromatic alcohols, in addition, can enumerate vinylbenzene, alpha-methyl styrene, the 1-vinyl naphthalene, the 3-vinyl toluene, the 4-propylstyrene, 4-phenylcyclohexane ethene, 4-dodecyl vinylbenzene, 2-ethyl-4-benzyl vinylbenzene, 4-(phenyl butyl) vinylbenzene, aromatic vinyls such as halogenated styrenes are monomer, vinyl cyanide, vinyl cyanides such as methacrylonitrile are monomer, divinyl, isoprene equiconjugate diene monomer etc., they can use separately or be used in combination more than 2 kinds, can be according to purpose or the suitable selection of purposes.
Be used to form the polyfunctional monomer of layer (I), it is the monomer that intramolecularly has 2 above carbon-to-carbon double bonds, for example comprise vinylformic acid, methacrylic acid, unsaturated monocarboxylic acid and vinyl carbinols such as styracin, the ester of unsaturated alcohols such as methylallyl alcohol, described unsaturated monocarboxylic acid and ethylene glycol, butyleneglycol, the ester of the dibasic alcohol of glycol such as hexylene glycol, phthalic acid, terephthalic acid, m-phthalic acid, ester of di-carboxylic acid such as toxilic acid and described unsaturated alcohol etc., specifically can enumerate allyl acrylate, the vinylformic acid first is for allyl ester, allyl methacrylate(AMA), methyl methacrylate is for allyl ester, allyl cinnamate, the styracin first is for allyl ester, diallyl maleate, Phthalic acid, diallyl ester, diallyl p phthalate, diallyl isophthalate, Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, butyleneglycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate etc., they can use separately or be used in combination more than 2 kinds, can be according to purpose or the suitable selection of purposes, wherein, special preferable methyl allyl acrylate.Here, the meaning of described " two (methyl) acrylate " is the general name of " diacrylate " and " two (methyl) acrylate ".
The layer (II) of the acrylic acid series multilayer structure polymer particle (A) that uses among the present invention should be for (ii) being formed by methacrylic ester 40～100 quality % and the monomer (mixture) that can constitute with other monomer 60～0 quality % of this methacrylic ester copolymerization by polymerization.The ratio of this monomer (mixture) methacrylic ester (ii) is preferred 60～99 quality %, further preferred 80～99 quality %.The ratio of methacrylic ester is during less than 40 quality %, and the photostabilization of acrylic acid series multilayer structure polymer particle (A) becomes insufficient.
Object lesson as the methacrylic ester that is used to form layer (II), can enumerate methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid pentyl ester, N-Hexyl methacrylate, Octyl methacrylate, methacrylic acid 2-ethylhexyl, cyclohexyl methacrylate, lauryl methacrylate, methacrylic acid tetradecyl ester, methacrylic acid palm ester, the methacrylic acid stearyl ester, methacrylic acid docosyl ester, the methacrylic acid stearyl, phenyl methacrylate, benzyl methacrylate etc., the preferable methyl methyl acrylate.
As be used to form the layer (II) can with other monomeric object lessons of this methacrylic ester copolymerization, can enumerate vinylformic acid and C such as methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, Octyl acrylate, 2-EHA, dodecylacrylate, vinylformic acid stearyl
1～C
18The ester of saturated fatty alcohol, vinylformic acid and C such as cyclohexyl acrylate
5Or C
6The ester of ester ring type alcohol, vinylbenzene, alpha-methyl styrene, the 1-vinyl naphthalene, the 3-vinyl toluene, the 4-propylstyrene, 4-phenylcyclohexane ethene, 4-dodecyl vinylbenzene, 2-ethyl-4-benzyl vinylbenzene, 4-(phenyl butyl) vinylbenzene, aromatic vinyls such as halogenated styrenes are monomer, vinyl cyanide, vinyl cyanides such as methacrylonitrile are monomer, maleimide, N-methyl maleimide, the N-ethyl maleimide, N-propyl group maleimide, N-sec.-propyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-(to bromophenyl) maleimide, maleimides such as N-(chlorophenyl) maleimide are monomer, the multi-functional monomer of representing in the above-mentioned example etc.Wherein, alkyl acrylates such as preferred methyl acrylate, ethyl propenoate, n-butyl acrylate.
For the acrylic acid series multilayer structure polymer particle (A) that uses among the present invention, can in the scope of above-mentioned monomeric kind and usage ratio, select suitable condition respectively, layer (I) is made of the component of polymer with caoutchouc elasticity, and layer (II) constitutes by having thermoplastic component of polymer.
With regard to the acrylic acid series multilayer structure polymer particle (A) that uses among the present invention, in the layer that wherein contains (II), at least constituent particle outermost (being total to) polymkeric substance, its number-average molecular weight of measuring according to GPC (gel permeation chromatography) method should be for below 30,000.Number-average molecular weight surpasses at 30,000 o'clock, has the situation of the melt fluidity decline of acrylic acid series multilayer structure polymer particle (A).About the lower limit of number-average molecular weight, do not have strict restriction, but the aspect of acrylic acid series multilayer structure polymer particle (A) technology trafficability characteristic is considered from production technique, preferred number average molecular weight is not less than 1,000.The aspect of the technology trafficability characteristic from obtain elastic recovery and production technique is simultaneously considered, is especially preferably made number-average molecular weight 3,000～20, in 000 the scope.
The median size of the acrylic acid series multilayer structure polymer particle (A) that uses among the present invention should be as below the 150nm.When the median size of acrylic acid series multilayer structure polymer particle (A) surpasses 150nm, there is the inadequate situation of melt fluidity.Lower value about median size is not particularly limited, but considers that from the viewpoint of the layer structure of the regulation that forms acrylic acid series multilayer structure polymer particle (A) preferably median size is more than the 30nm.Further preferred median size is 80～120nm.
As the acrylic acid series multilayer structure polymer particle (A) that uses among the present invention, particularly consider from rerum natura aspect and manufacturing simplicity aspect, be preferably at penetralia and have the rubber constituent layer (Ia) that forms by monomer mixture (ia), have the rubber constituent layer (Ib) that constitutes by monomer mixture (ib) in the adjacency section that is positioned at the state that covers this rubber constituent layer (Ia) outer surface, and have the such 3-tier architecture of thermoplastic resin component layer (II) that (ii) forms by monomer (mixture) in most external.As be used to form layer (Ia) and an acrylate (Ib), polyfunctional monomer and can with other monofunctional monomers of this acrylic ester copolymer, can use and be used to form described layer of (I) identical monomer.
Use in the composition for thermoplastic elastomer that the acrylic acid series multilayer structure polymer particle (A) of above-mentioned optimal way obtains, in order to obtain good resistance to tearing and good flexibility and other mechanical properties simultaneously, the containing ratio (quality %) of the acrylate in the preferred monomers mixture (ia) and the containing ratio (quality %) of the acrylate in the monomer mixture (ib) poor [(ia) (and unit: quality %)-(ib) (unit: quality %) or (ib) (unit: quality %)-(ia) (unit: quality %)] become the above value of 3 quality %, more preferably [(ia) (unit: quality %)-(ib)] becomes the above value of 3 quality %.
In addition, in the acrylic acid series multilayer structure polymer particle (A) of above-mentioned optimal way, the mass ratio [(Ia)/(Ib)] of rubber constituent layer (Ia) and rubber constituent layer (Ib) is preferred 5/95～95/5, more preferably 20/80～80/20.Mass ratio [(Ia)/(Ib)] is in 5/95～95/5 the scope time, generally can obtain the flexibility of good resistance to tearing and appropriateness and mechanical properties in addition simultaneously.
Wherein, the acrylic acid series multilayer structure polymer particle (A) of above-mentioned optimal way is, with the rubber constituent layer (Ib) of inner most rubber constituent layer (Ia), its adjacency section, and such 3 layers of outermost thermoplastic resin component layer (II) as basic comprising, also can be between layer (Ib) and layer (II) any polymer layer of existence more than 1 layer.Just, want to bring into play especially significantly effect of the present invention, then the quality sum of preferred rubber component layer (Ia), rubber constituent layer (Ib) and thermoplastic resin component layer (II) is more than 80% quality with respect to all quality of acrylic acid series multilayer structure polymer particle (A), and more preferably acrylic acid series multilayer structure polymer particle (A) only is made of rubber constituent layer (Ia), rubber constituent layer (Ib) and thermoplastic resin component layer (II).
The acrylic acid series multilayer structure polymer particle (A) that uses among the present invention, can according to known be used for making have at least 1 layer of rubber constituent layer by inside, and most external has the manufacture method manufacturing of the acrylic acid series multilayer structure polymer particle that the such layer more than 2 layers of at least 1 layer of thermoplastic resin component layer constitutes, its order by according to the rules is used for forming the polymerization technology of rubber constituent layer and is used for forming the polymerization technology of thermoplastic resin component layer, from central division to outside form layers in turn.Be not particularly limited about the polymerization that is used for making the acrylic acid series multilayer structure polymer particle (A) that the present invention uses, for example, the known polymerization process of acrylic acid series multilayer structure polymer particle be can make according to common being used to, emulsion polymerization, suspension polymerization, solution polymerization process or their combination adopted.For example, can by forming the polymerization of each layer, obtain acrylic acid series multilayer structure polymer particle (A) according to known means in the letex polymerization.At this moment, note following aspect.
(1) be used to form in the polymerization technology (a) of rubber constituent layer (I), copolymerization is by acrylate 50～99.99 quality %, the monomer mixture (i) that can constitute with other monofunctional monomers 49.99～0 quality % and polyfunctional monomer 0.01～10 quality % of this acrylic ester copolymer.
(2) be used to form in the polymerization technology (b) of thermoplastic resin component layer (II), polymerization by methacrylic ester 40～100 quality % and the monomer (mixture) that can constitute with other monomers 60～0 quality % of this acrylic ester copolymer (ii).
(3) in this polymerization technology (b), be used to form in the polymerization technology of outermost at least thermoplastic resin component layer (II), preferably (ii) use molecular weight regulator to carry out polyreaction with the ratio of 0.4～10 quality % with respect to monomer (mixture).
(4) make the ratio [(i)/(ii)] of the total quality of the monomer mixture (i) that uses in the total polymerization reaction process and monomer (mixture) total quality (ii) in 30/70～90/10 scope.
The median size of the acrylic acid series multilayer structure polymer particle (A) when (5) whole polymerization technologies being finished is below the 150nm, for example can control by the usage quantity of emulsifying agent.
Wherein, when making acrylic acid series multilayer structure polymer particle usually, the usage ratio of the molecular weight regulator that uses in order to form outermost thermoplastic resin component layer is about 0～0.3 quality % with respect to monomer mixture.But, when making acrylic acid series multilayer structure polymer particle of the present invention (A), if the usage ratio of molecular weight regulator is less than 0.4 quality %, the number-average molecular weight of thermoplastic resin composition that then constitutes this layer is too high, exists by composition for thermoplastic elastomer of the present invention the be shaped elastic recovery or the mobile inadequate situation that is shaped of the molding that obtains.In addition, when making acrylic acid series multilayer structure polymer particle (A), the ratio of molecular weight regulator promptly is enough to up to 10 quality % with respect to monomer mixture, even use more, there is not further to improve the effect of elastic recovery yet, the residual ratio of the molecular weight regulator in the acrylic acid series multilayer structure polymer particle (A) is uprised, therefore do not expect.The ratio of molecular weight regulator, with respect to monomer (mixture) (ii), in preferred 0.4～5 quality % scope, more preferably in 0.6～2 quality % scope.
Object lesson as molecular weight regulator, can enumerate thio-alcohols such as n-octyl mercaptan, tert octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, mercaptoethanol, the terpene blend that terpinolene, limonene, uncle's terpinene and a small amount of other ring-type terpenes constitute, halohydrocarbon such as chloroform, tetracol phenixin etc.Alkyl sulfhydryls such as wherein preferred n-octyl mercaptan.
Temperature during letex polymerization is unqualified, but general range is 0～100 ℃.As emulsifying agent used herein, can enumerate an alkali metal salt of lipid acid such as sodium oleate, sodium laurate, sodium stearate, the sulfuric acid of Fatty Alcohol(C12-C14 and C12-C18) such as sodium lauryl sulphate, rosinates such as resin acid potassium, alkylaryl sulphonates such as Sodium dodecylbenzene sulfonate etc., phosphate ester salts such as polyxyethylated sodium phosphate, they can use being used in combination more than a kind or 2 kinds.
Polymerization starter as using in the letex polymerization is generally radical polymerization initiator.As the object lesson of radical polymerization initiator, can use persulphates such as Potassium Persulphate, ammonium persulphate, superoxide such as Diisopropyl azodicarboxylate, benzoyl peroxide separately.In addition, as radical polymerization initiator, also can use hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide, hydrogen peroxide to reducto oxydative system polymerization starter that the Meng, reductive agent such as organic hydroperoxide class such as alkane and transition metal salt was combined to form.
In addition, about from polyreaction system, separating the method that obtains the acrylic acid series multilayer structure polymer particle (A) that generates after the letex polymerization, can carry out according to known method, for example, can adopt acid-precipitation method, salting-out process, spray-drying process, cryocoagulation method etc.Wherein, separate the acrylic acid series multilayer structure polymer particle (A) that obtains, even at the outermost layer that is made of the thermoplastic resin composition, it is also harmless that the part adhesion takes place between particle mutually.
Among the present invention, the content of ethylene vinyl acetate copolymer (B) with respect to acrylic acid series multilayer structure polymer particle (A) 100 mass parts, should be 5～300 mass parts, preferred 10～200 mass parts, further preferred 30～120 mass parts.The content of ethylene vinyl acetate copolymer (B) is during less than 5 mass parts, the effect of the tear strength that ethylene vinyl acetate copolymer (B) has is insufficient, when surpassing 300 mass parts, the good photostabilization that acrylic acid series multilayer structure polymer particle (A) has can't be brought into play, is unfavorable therefore.
The ethylene vinyl acetate copolymer of using among the present invention (B) is not so long as damage the material of effect of the present invention and then be not particularly limited, for example, consider optimal ethylene-vinyl acetate between to for plastic random copolymers from the aspect of the transparency of flexibility, forming process, molding.When using the ethene-vinyl acetate random copolymers as ethylene vinyl acetate copolymer (B), the content of the ethylene unit of this multipolymer is preferred 95～60 quality %, further preferred 85～70 quality %.
The grafting of using among the present invention on the main chain that is made of ethylene vinyl acetate copolymer is higher than the content of the graft copolymer (C) that the monomeric unit of this main chain forms in conjunction with polarity, with respect to acrylic acid series multilayer structure polymer particle (A) 100 mass parts, should be 0.5～150 mass parts, preferred 1～100 mass parts, further preferred 2～40 mass parts.Albinism takes place during less than 0.5 mass parts in the content of graft copolymer (C) when the composition for thermoplastic elastomer that obtains stretches, when surpassing 150 mass parts, the effect of being added does not change, and causes cost to increase on the contrary.
The ethylene unit of the ethylene vinyl acetate copolymer of the main chain of formation graft copolymer (C) and the mass ratio of vinyl acetate unit are preferred 95: 5～60: 40.
The graft copolymer that uses among the present invention (C) is preferably, grafting be combined in monomeric unit on its main chain be from (methyl) acrylic ester monomeric unit, Vinyl Ether be monomeric unit, (methyl) acrylamide monomeric unit, and the acrylic monomeric unit select more than at least a kind.
Monomeric unit as the ethylene vinyl acetate copolymer of the main chain that constitutes graft copolymer (C), then be not particularly limited so long as do not damage the material of effect of the present invention, mainly constitute by ethene and vinyl-acetic ester, for example, so long as following a small amount of of 20 quality %, can contain by other monomers such as propylene, divinyl, isoprene, iso-butylene constitute unitary more than a kind or 2 kinds.Wherein, when this monomeric unit was divinyl, isoprene equiconjugate diene, part or all of the unsaturated double-bond of preferred polymers block (Block ロ Star Network) was by hydrogenation.
Be combined in polarity on the main chain of graft copolymer (C) as grafting and be higher than the example of the monomeric unit of this main chain, can enumerate (methyl) acrylic ester monomeric unit, Vinyl Ether is a monomeric unit, (methyl) acrylamide monomeric unit, and the acrylic monomeric unit etc., for example, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) dodecylacrylate, (methyl) alkyl acrylates such as (methyl) 2-EHA, vinyl acetate, vinyl acetate such as pivalic vinyl acetate, (methyl) acrylamide, (methyl) vinyl cyanide etc., they can use separately or be used in combination more than 2 kinds, wherein, preferable methyl methyl acrylate, ethyl propenoate, butyl acrylate, vinyl cyanide.
In addition, in grafting bonded monomeric unit, also can contain have from carboxyl, epoxy group(ing), acid anhydride, and amino the vinyl monomer unit of at least a kind of functional group selecting.With respect to graft copolymer (C), above-mentioned introducing amount by grafting bonded monomeric unit is preferred 10～60 quality %.
The number-average molecular weight of ethylene vinyl acetate copolymer of using among the present invention (B) and graft copolymer (C) is, then be not particularly limited so long as do not damage the material of effect of the present invention, for example, consider that from the aspect of the transparency of flexibility, forming process, molding the value of being measured by the GPC method is preferably 20,000～2,000,000.
In the composition for thermoplastic elastomer of the present invention, in the scope of not damaging effect of the present invention, can cooperate more than a kind or 2 kinds of various rerum natura activators as required, to improve the rerum natura of molding, film or thin slice that its shaping is obtained.Such rerum natura activator is not particularly limited, and for example, can comprise additive kinds such as oxidation inhibitor, UV light absorber, lubricant.Particularly, can enumerate oxidation inhibitor, thermo-stabilizer, photostabilizer, UV light absorber, neutralizing agent, lubricant, antifogging agent, anti, paraffin oil, slip(ping)agent, linking agent, crosslinking coagent, tinting material, fire retardant, dispersion agent, antistatic agent etc.
Composition for thermoplastic elastomer of the present invention, can pass through acrylic acid series multilayer structure polymer particle (A), ethylene vinyl acetate copolymer (B), graft copolymer (C), or further add other resins or rerum natura activator etc. as required, mix, and/or mix and make, mix after preferred the mixing.At this moment, tumbler mixer, mixing machine, stirrer etc. can be used, screw extrusion press can be used as muller as mixing machine.
Forming and machining method as composition for thermoplastic elastomer of the present invention, for example can or extrude moulding methodes such as extrusion molding, injection forming, blow molding, blowing, press molding, calendaring molding, fusion stacking shaping, hollow forming, compression molding, vacuum forming, foaming and molding such as thin slice shaping, form the molding of arbitrary shapes such as Powdered, particulate state, tabular, film or laminar, tubulose, hollow form, case shape by special-shaped extrusion molding.Molding is general owing to its good flexibility, is applicable in the soft parts in fields such as trolley part, household electrical appliances parts, wire outer skin, medical treatment product, groceries, footwear.In addition, because the cementability of composition for thermoplastic elastomer of the present invention and other resins is good, so can be used as the soft parts use of the soft layer or the composite molded product of duplexer.
About the film that obtains by composition for thermoplastic elastomer of the present invention or the thickness of thin slice, be not particularly limited, but be generally about 1000～20 μ m, particularly can easily obtain the material of the thin thickness about 300～20 μ m.
The film or the thin slice that constitute by composition for thermoplastic elastomer of the present invention, be applicable to means of agricultural production materials such as agricultural film, label film (マ one キ Application グ Off イ Le system), decorating film designability thin slices such as (changing make-up Off イ Le system), dicing sheet (ダ イ シ Application グ シ one ト), background thin slice industrial thin slices such as (バ Star Network グ ラ イ Application De シ one ト), various packaging films, mat applying (デ ス Network マ Star ト), dividing plate (Inter bodyguard are cut り) etc. general thin slice etc.
Composite molded product of the present invention is, has the part that constitutes by composition for thermoplastic elastomer of the present invention in its at least a portion, and the molding that has the part that constitutes by other materials in other parts, the preferably soft part that constitutes by composition for thermoplastic elastomer of the present invention by heat bonding and be higher than the material that hard portion that the thermoplastic resin of this soft part constitutes forms by hardness.The thermoplastic resin that is higher than this soft part as hardness, for example, can enumerate phenylethylene resin series, acrylic resin, polyester based resin, polyamide-based resin, polyacetal and be resin, polycarbonate, ethene is ionomer and polyvinylidene difluoride (PVDF) etc., is not particularly limited.Composite molded product of the present invention is for example, to be applicable to fields such as material of construction, furniture material, electrical and electronic parts, agriculture engineering materials, vehicle material, pipe flexible pipe, daily necessities groceries stationery.
Embodiment
Below by Production Example, embodiment and comparative example the present invention is specifically described, but the present invention is not limited to these.Wherein, according to each measured value in following evaluation method evaluation Production Example, embodiment and the comparative example.
(1) median size of acrylic acid series multilayer structure polymer particle (A)
The median size of acrylic acid series multilayer structure polymer particle (A) is, the sample of taking the emulsion of use after polymerization finishes, utilize laser particle size analysis device PAR-III (Otsuka Electronics Co., Ltd. system), by dynamic light scattering determination, try to achieve with the accumulative analysis.
(2) the outermost number-average molecular weight of acrylic acid series multilayer structure polymer particle (A)
Constitute the number-average molecular weight of the outermost component of polymer of acrylic acid series multilayer structure polymer particle (A), be with acrylic acid series multilayer structure polymer particle (A) sample after in toluene, fully stirring under the room temperature, centrifugation, the solution that use obtains, measure with the GPC method, with the value that obtains thus as the number-average molecular weight that constitutes outermost polymkeric substance among the present invention.
(3) measurement of hardness
Use A type hardness tester meter (オ ス カ one system), measure based on JIS K6253.
(4) tear strength test
Use self-registering instrument ((strain) Shimadzu Seisakusho Ltd. system),, make the dihedral test piece of non-incision, under the condition of 100mm/min, measure tear strength based on JIS K6252.
(5) tension test
Make No. 3 dumbbell test pieces,, use self-registering instrument ((strain) Shimadzu Seisakusho Ltd. system),, under 200mm/ minute condition, measure tensile elongation based on JIS K6301 with this dumbbell test piece.
(6) light fastness test
Use the Exposure to Sunlight weather colour fastness instrument S80 of ス ガ trier (strain) system, under 63 ℃ of blackboard temperatures, humidity 50%, 18 minutes/2 hours condition of spray circulation, the acceleration of the carrying out 2000 hours test of being exposed to the sun is to estimate with respect to the conservation rate (the back draft length of being exposed to the sun conservation rate) of the tensile elongation after the test before the test.
(7) stretching albefaction
Under above-mentioned tension test condition, the albefaction degree of the stretched portion that stretched 30% o'clock according to following judgment standard visual assessment.
Zero: do not have albefaction fully
△: some albefactions are arranged
*: albefaction
In addition, monomer name of using in the Production Example and abbreviation thereof [() in] are as shown in following.
Methyl methacrylate (MMA), n-butyl acrylate (BA), methyl acrylate (MA), vinylbenzene (St), allyl methacrylate(AMA) (ALMA).
In following embodiment and comparative example, ethylene vinyl acetate copolymer (B) and on the main chain that constitutes by ethylene vinyl acetate copolymer grafting be higher than the graft copolymer (C) that the monomeric unit of this main chain forms in conjunction with polarity, be to use following material.
1. ethylene vinyl acetate copolymer (B) [below, slightly be designated as EVA].
Use " the ウ Le ト ラ セ Application 635 " of eastern ソ-(strain) system.These goods are ethylene-vinyl acetate copolymer.
2. be higher than the graft copolymer (C) that the monomeric unit of this main chain forms [below, slightly be designated as EVA-g-PMMA] in conjunction with polarity in grafting on the main chain that constitutes by ethylene vinyl acetate copolymer.
Use " モ デ イ パ one A6200 " of Japanese grease (strain) system.These goods are as the main chain composition, with the graft copolymer of polymethylmethacrylate (30 quality %) as branched-chain component with EVA (70 quality %).
The manufacturing of Production Example 1[acrylic acid series multilayer structure polymer particle (A-1)]
Under nitrogen environment, in the polymerizer that agitating vane, cooling tube and dropping funnel are installed, add distilled water 200 mass parts, the new general lux of emulsifying agent (ネ オ ペ レ Star Network ス) F-25[flower king (strain) system] 0.6 mass parts, and yellow soda ash 0.1 mass parts, be heated to 80 ℃ and make its dissolving evenly.Then, under uniform temp, after adding potassium peroxydisulfate 0.05 mass parts, from dropping funnel with dripped in 1 hour by BA 29.8 mass parts, MMA 13.5 mass parts, St 6.5 mass parts, ALMA 0.2 mass parts, and as ア デ カ コ one Le CS-141E[rising sun electrification (strain) system of emulsifying agent] mixture that 0.25 mass parts is formed, form the 1st layer.After dripping off, under uniform temp, continue reaction 1 hour, confirm that with gas-chromatography each monomer all is consumed.
Then, after in the copolymer emulsion that obtains, adding potassium peroxydisulfate 0.025 mass parts, from dropping funnel with dripped in 30 minutes by BA 19.9 mass parts, MMA 0.5 mass parts, St 4.5 mass parts, ALMA 0.1 mass parts, and as ア デ カ コ one Le CS-141E[rising sun electrification (strain) system of emulsifying agent] mixture that 0.125 mass parts is formed, form the 2nd layer.After dripping off, continue reaction 1 hour, confirm that with gas-chromatography each monomer all is consumed at 80 ℃.
Further, after in the copolymer emulsion that obtains, adding potassium peroxydisulfate 0.025 mass parts, from dropping funnel with dripping in 30 minutes by MMA 23.75 mass parts, MA 1.25 mass parts, n-octyl mercaptan 0.25 mass parts and as ア デ カ コ one Le CS-141E[rising sun electrification (strain) system of emulsifying agent] mixture that 0.125 mass parts is formed, form the 3rd layer.After dripping off, further continue reaction 1 hour, confirm that with gas-chromatography each monomer all is consumed, finish polymerization at 80 ℃.The median size of the acrylic acid series multilayer structure polymer particle (A-1) that obtains is 104nm.
, after-20 ℃ of coolings freezing aggegation in 5 hours, melt for this emulsion, and take out agglutinator, clean 3 times with 40 ℃ of hot water.60 ℃ of following drying under reduced pressure 2 days, obtain the pulverous 3 stratotype acrylic acid series multilayer structure polymer particles (A-1) of aggegation.Wherein, the number-average molecular weight that constitutes outermost component of polymer is 18,000.Summary is as shown in table 1.
The manufacturing of Production Example 2[acrylic acid series multilayer structure polymer particle (A-2)]
Under nitrogen environment, in the polymerizer that agitating vane, cooling tube and dropping funnel are installed, add distilled water 200 mass parts, Sodium dodecylbenzene sulfonate 1 mass parts and yellow soda ash 0.05 mass parts, be heated to 80 ℃ and make its uniform dissolution.Then, after adding potassium peroxydisulfate 0.01 mass parts, from dropping funnel,, form the 1st layer with the monomer mixture that dripped continuously and form in 20 minutes by MMA 9.48 mass parts, BA 0.5 mass parts and ALMA0.02 mass parts.After dripping off, under uniform temp, continue reaction 30 minutes, confirm that with gas-chromatography each monomer all is consumed.
Then, in the copolymer emulsion that obtains, add potassium peroxydisulfate 0.03 mass parts after, with dripping by MMA 1.34 mass parts, BA 25.85 mass parts continuously in 40 minutes, reaching the mixture that ALMA 0.81 mass parts is formed, form the 2nd layer.After dripping off, further continue reaction 30 minutes, confirm that with gas-chromatography each monomer all is consumed at 80 ℃.
Further, in the copolymer emulsion that obtains, add potassium peroxydisulfate 0.06 mass parts after, from dropping funnel,, form the 3rd layer with the mixture that dripped and form in 100 minutes by MMA 55.8 mass parts, BA 6.2 mass parts and n-octyl mercaptan 0.3 mass parts.After dripping off, continue reaction 1 hour, confirm that with gas-chromatography each monomer all is consumed, finish polymerization at 80 ℃.The median size of the acrylic acid series multilayer structure polymer particle (A-2) in the emulsion that obtains is 99nm.
, after-20 ℃ of coolings freezing aggegation in 5 hours, melt for this emulsion, and take out agglutinator, clean 3 times with 80 ℃ of hot water.70 ℃ of drying under reduced pressure 2 days, obtain the pulverous 3 stratotype acrylic acid series multilayer structure polymer particles (A-2) of aggegation.Wherein, the number-average molecular weight that constitutes outermost component of polymer is 98,000.Summary is as shown in table 1.
The manufacturing of Production Example 3[acrylic acid series multilayer structure polymer particle (A-3)]
Except with in the Production Example 1, the n-octyl mercaptan of the monomer mixture when forming outermost layer becomes outside 0.125 mass parts, carries out polymerization in the same manner with Production Example 1.The median size of the acrylic acid series multilayer structure polymer particle (A-3) that obtains is 104nm, and the number-average molecular weight that constitutes the outermost component of polymer of this particle is 98,000.Summary is as shown in table 1.
Table 1
| The 1st stage polymer (quality %) | The 2nd stage polymer (quality %) | The 3rd stage polymer (quality %) | Median size (nm) | Number-average molecular weight | |
| Production Example 1 (A-1) | BA/MMA/St/ALMA (59.6/27.0/13.0/0.4) 50 mass parts | BA/MMA/St/ALMA (79.6/2.0/18.0/0.4) 25 mass parts | MMA/MA (95.0/5.0) 25 mass parts | 104 | 18000 |
| Production Example 2 (A-2) | MMA/BA/ALMA (94.8/5.0/0.2) 10 mass parts | MMA/BA/ALMA (4.8/92.3/2.9) 28 mass parts | MMA/BA (90.0/10.0) 62 mass parts | 99 | 98000 |
| Production Example 3 (A-3) | BA/MMA/St/ALMA (59.6/27.0/13.0/0.4) 50 mass parts | BA/MMA/St/ALMA (79.6/2.0/18.0/0.4) 25 mass parts | MMA/MA (95.0/5.0) 25 mass parts | 104 | 98000 |
Embodiment 1～3, comparative example 3,5,7
With pulverous 3 stratotype acrylic acid series multilayer structure polymer particles (A-1) of obtaining in the Production Example 1, EVA, and EVA-g-PMMA mix according to the amount of table 2 record, use 25 Φ twin screw degassing extruders, under 200 ℃, carry out granulation.For the particle that obtains, under 200 ℃, be made into the thin slice of thickness 1mm with compressing forming machine, carry out various mensuration.The measurement result that obtains is as shown in table 2.
Comparative example 1
Pulverous 3 stratotype acrylic acid series multilayer structure polymer particles (A-1) with obtaining in the Production Example 1 use 25 Φ twin screw degassing extruders, in 200 ℃ of following granulations.For the particle that obtains, under 200 ℃, be made into the thin slice of thickness 1mm with compressing forming machine, carry out various mensuration.The measurement result that obtains is as shown in table 2.
Comparative example 2
Among the embodiment 1, the 3 stratotype acrylic acid series multilayer structure polymer particles (A-2) that obtain in using Production Example 2 replace making thin slice similarly to Example 1 the 3 stratotype acrylic acid series multilayer structure polymer particles (A-1), carry out various mensuration.The measurement result that obtains is as shown in table 2.
Comparative example 4
Among the embodiment 1,, make thin slice similarly to Example 1, carry out various mensuration except not containing the EVA-g-PMMA.The measurement result that obtains is as shown in table 2.
Comparative example 6
Among the embodiment 1,, make thin slice similarly to Example 1, carry out various mensuration except not containing the EVA.The measurement result that obtains is as shown in table 2.
Comparative example 8
Among the embodiment 1, the 3 stratotype acrylic acid series multilayer structure polymer particles (A-3) that obtain in using Production Example 3 replace making thin slice similarly to Example 1 the 3 stratotype acrylic acid series multilayer structure polymer particles (A-1), carry out various mensuration.The result who obtains is as shown in table 2.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | ||
| (A-1) | Mass parts | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | ||
| (A-2) | Mass parts | 100 | ||||||||||
| (A-3) | Mass parts | 100 | ||||||||||
| EVA | Mass parts | 40 | 100 | 40 | 40 | 5 | 40 | 40 | 4000 | 40 | ||
| EVA-g-PMMA | Mass parts | 5 | 5 | 30 | 5 | 5 | 0.3 | 5 | 10 | 5 | ||
| Hardness (JIS-A) | - | 74 | 80 | 89 | 70 | ＞95 | 73 | 75 | 76 | 72 | 93 | ＞95 |
| Tear strength | N/cm | 365 | 430 | 380 | 190 | 450 | 195 | 350 | 360 | 200 | 200 | 390 |
| The back draft length of being exposed to the sun conservation rate | ％ | 85 | 80 | 85 | 92 | 86 | 90 | 83 | 82 | 90 | 15 | 85 |
| The stretching albefaction | - | ○ | ○ | ○ | ○ | ○ | ○ | × | △ | ○ | ○ | ○ |
Result according to table 2 can learn that the embodiment 1～3 that all satisfies the technical characterictic of invention compares with the comparative example 3 of the technical characterictic of containing of the comparative example 1 that does not contain EVA and EVA-g-PMMA, EVA of proportional discontented unabridged version invention, and tear strength is improved.
In addition, result according to table 2 can learn, used the comparative example 2 of acrylic acid series multilayer structure polymer particle (A-2), because the technical characterictic of the discontented unabridged version invention of the ratio [(I)/(II)] of the total quality of the outermost number-average molecular weight in the thermoplastic resin component layer (II) and the quality of rubber constituent layer (I) and thermoplastic resin component layer (II), therefore with respect to the embodiment 1 that satisfies this feature, its flexibility is poor.In addition, used the comparative example 8 of acrylic acid series multilayer structure polymer particle (A-3), because the technical characterictic of the discontented unabridged version invention of the outermost number-average molecular weight in the thermoplastic resin component layer (II), therefore with respect to the embodiment 1 that satisfies this feature, its flexibility is poor.
Further, the result according to table 2 can learn that embodiment 1 compares with comparative example 5 with the comparative example 4 of the technical characterictic of containing of EVA-g-PMMA of proportional discontented unabridged version invention, has improved the stretching albefaction.
Further, the result according to table 2 can learn that embodiment 1 compares with comparative example 7 with the comparative example 6 of the technical characterictic of containing of EVA of proportional discontented unabridged version invention, has improved tear strength, particularly, compares with comparative example 7, has also been paid flexibility.
Industrial application possibility
According to the present invention, can provide light resistance, flexibility good, and after making film the large composition for thermoplastic elastomer of its tearing strength. By formed products, film or the thin slice that said composition is shaped and obtains, be applicable to the soft material in the fields such as automobile component, household electrical appliances parts, wire outer skin, medical supplies, groceries, footwear. In addition, because the cementability of composition for thermoplastic elastomer of the present invention and other resins is good, so can also be used as the soft layer of duplexer or the soft parts of composite molded product.
Claims (6)
1. composition for thermoplastic elastomer, contain acrylic acid series multilayer structure polymer particle (A) 100 mass parts, ethylene vinyl acetate copolymer (B) 5～300 mass parts, and on the main chain that constitutes by ethylene vinyl acetate copolymer grafting be higher than graft copolymer (C) 0.5～150 mass parts that the monomeric unit of this main chain forms in conjunction with polarity, wherein
(a) this acrylic acid series multilayer structure polymer particle (A) is, has at least 1 layer of rubber constituent layer (I) by inside, and outermost layer has the such layer more than 2 layers of at least 1 layer of thermoplastic resin component layer (II) and constitute,
(b) this rubber constituent layer (I) is, the polymer layer that forms by acrylate 50～99.99 quality %, the monomer mixture (i) that can constitute by copolymerization with other monofunctional monomers 49.99～0 quality % and polyfunctional monomer 0.01～10 quality % of this acrylic ester copolymer
(c) this thermoplastic resin component layer (II) is, the polymer layer that (ii) forms by methacrylic ester 40～100 quality % and the monomer that can constitute by polymerization with other monomer 60～0 quality % of this methacrylic ester copolymerization,
(d) in this thermoplastic resin component layer (II), the number-average molecular weight of the outermost layer polymkeric substance of measuring with the GPC method is below 30,000,
(e) ratio [(I)/(II)] of the total quality of the total quality of this rubber constituent layer (I) and this thermoplastic resin component layer (II) is 30/70～90/10,
(f) median size of this acrylic acid series multilayer structure polymer particle (A) is below the 150nm.
2. according to the composition for thermoplastic elastomer of claim 1 record, wherein, on the main chain of graft copolymer (C) grafting bonded monomeric unit for from (methyl) acrylic ester monomeric unit, Vinyl Ether be select monomeric unit, (methyl) acrylamide monomeric unit, the acrylic monomeric unit more than at least a kind.
3. according to the composition for thermoplastic elastomer of claim 2 record, wherein, grafting bonded monomeric unit is a methyl methacrylate units on the main chain of graft copolymer (C).
4. the molding that constitutes by the composition for thermoplastic elastomer of claim 1 record.
5. film or the thin slice that constitutes by the composition for thermoplastic elastomer of claim 1 record.
6. the composite molded product that has the part that the composition for thermoplastic elastomer by claim 1 record constitutes.
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| JP2004129386 | 2004-04-26 | ||
| JP129386/2004 | 2004-04-26 |
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| US (1) | US7569638B2 (en) |
| EP (1) | EP1752493B1 (en) |
| JP (1) | JP4818914B2 (en) |
| CN (1) | CN100540602C (en) |
| AT (1) | ATE402979T1 (en) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107938070A (en) * | 2017-12-08 | 2018-04-20 | 南通元创卓宇纺织品有限公司 | A kind of moisture absorbing and sweat releasing cotton spinning yarn and its production method |
| CN107938071A (en) * | 2017-12-08 | 2018-04-20 | 南通元创卓宇纺织品有限公司 | A kind of high resiliency cotton spinning line and its production method |
| CN108118414A (en) * | 2017-12-08 | 2018-06-05 | 南通元创卓宇纺织品有限公司 | A kind of high tight ness rating cotton spinning line and its production method |
| CN115698170A (en) * | 2020-07-01 | 2023-02-03 | 陶氏环球技术有限责任公司 | Heat and oil resistant composition |
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| US10654962B2 (en) * | 2012-09-07 | 2020-05-19 | Mitsubishi Chemical Corporation | Acrylic film, method for producing same, laminate film, laminated injection molded article, and method for producing rubber-containing polymer |
| EP3616910A4 (en) * | 2017-04-28 | 2021-01-27 | Kuraray Co., Ltd. | Thermoplastic resin multilayer film, method for manufacturing same, and laminate |
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| TW555807B (en) * | 2000-05-03 | 2003-10-01 | Rohm & Haas | Polymeric compositions and processes for providing weatherable film and sheet |
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- 2005-04-25 AT AT05734597T patent/ATE402979T1/en not_active IP Right Cessation
- 2005-04-25 JP JP2006519506A patent/JP4818914B2/en not_active Expired - Fee Related
- 2005-04-25 WO PCT/JP2005/007768 patent/WO2005103144A1/en active IP Right Grant
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- 2005-04-25 EP EP05734597A patent/EP1752493B1/en not_active Not-in-force
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107938070A (en) * | 2017-12-08 | 2018-04-20 | 南通元创卓宇纺织品有限公司 | A kind of moisture absorbing and sweat releasing cotton spinning yarn and its production method |
| CN107938071A (en) * | 2017-12-08 | 2018-04-20 | 南通元创卓宇纺织品有限公司 | A kind of high resiliency cotton spinning line and its production method |
| CN108118414A (en) * | 2017-12-08 | 2018-06-05 | 南通元创卓宇纺织品有限公司 | A kind of high tight ness rating cotton spinning line and its production method |
| CN115698170A (en) * | 2020-07-01 | 2023-02-03 | 陶氏环球技术有限责任公司 | Heat and oil resistant composition |
Also Published As
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| DE602005008586D1 (en) | 2008-09-11 |
| EP1752493A4 (en) | 2007-10-03 |
| WO2005103144A1 (en) | 2005-11-03 |
| US7569638B2 (en) | 2009-08-04 |
| EP1752493B1 (en) | 2008-07-30 |
| EP1752493A1 (en) | 2007-02-14 |
| US20070225418A1 (en) | 2007-09-27 |
| JPWO2005103144A1 (en) | 2008-03-13 |
| CN100540602C (en) | 2009-09-16 |
| JP4818914B2 (en) | 2011-11-16 |
| ATE402979T1 (en) | 2008-08-15 |
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